Esters derived from petroleum hydrocarbons and method of producing same



Patented Feb. 7, 1933 UNITED STATES PATENT OFFICE- HERMAN A. BRUSON, F GERMANTOWN, PENNSYLVANIA, ASSIGNOB TO THE BESINOUS PRODUCTS 65 CHEMICAL CO. INC.,

mans mmrvm: rnou rn'raorluum A CORPORATION OF DELAWARE EYDBOCABBONS AND METHOD OF PBbDUGING SAME R0 Drawing. Application filed December 10, 1929, Serial No. 413,138. Renewed December 16, 1982.

This invention relates to esters of the organic acids which are produced by condensation of petroleum hydrocarbons with anhydrides of polybasic acids.

In my co-pending Satent application, Se rial No. 398,823 filed ctober 10, 1929 I'have described in detail the above mentioned acids and have also described the process by which the may be prepared from petroleum oils suc as asoline, naphtha, kerosene, parafiin oil and t e like.

The object of the present invention is to reduce new and useful esters of these aci s by heating them with pinene, or oils rich in pinene, notably turpentine, so as to 8 form what appear to be bornyl and iso-bornyl esters possessing the unusual properties of being amorphous, transparent masses well adapted for use as synthetic resins in coatinkg compositions, pyroxylin lacquers, and the When petroleum hydrocarbons such as gasoline, petroleum naphthas, kerosene, parafiin oils, Vaseline, araffin wax, refined petroleum lubricating oi s or even crude petroleum are heated with the anhydride of a polybasic or- 1ganic acid (phthalic anhydride, succinic anydride, maleic anhydride, and the like) in the presence of anhydrous aluminum chloride, and the resulting mass hydrolyzed with water, acid or alkali, there is obtained a complex mixture of organic acids as described in my above mentioned co-pending patent application, Serial No. 398,823.

These acids apparently contain one carboxyl group, one ketonic group and an alkyl radicle attached directly to the carbon atom of the ketonic group. This alkyl group consists of a plurality of methylene groups, the nature of which varies with the petroleum hydrocarbon that is employed in the Camdensation. A straight run Pennsylvania gasoline boiling between 60 and 200 C. consists essentially of aliphatic hexanes, heptanes and 5 octanes. When condensed with phthalic anhydride, such as gasoline yields an acid mixture consisting for the most part of acids havmg the general formula OOOH wherein R is an aliphatic oup containing respectively six, seven and elght carbon atoms of both normal and branched chain character. When higher boiling petroleum hydrocarbons such as kerosene, naphtha, parafiin, arafiin oil and the like, are used in place 0 the gasoline in the above condensation the num er of methylene groups in R of the above formula increases considerably since these latter hydrocarbons contain decanes, undecanes, pentadecanes and higheraliphatic hydrocarbons respectively.

It is evidc-r.v hat the complexity of the aclds derived from the aforementioned petroleum hydrocarbons in the manner indicated, precludes exact classification. They are hereafter referred to therefore as the ketonic acids obtained by condensing etroleum hydrocarbons with anhydrides o polybasic organic acids. This applies equally well to the acids derived from a similar condensation with etroleum hydrocarbons which are essentia ly of naphthenic character, such as shale 011 hydrocarbons and distillates from Russian or Californian petroleums.

The present invention consists in heatin any of the ketonic acids obtained as described above by the process disclosed in my co-pending patent application, Serial No. 398,823, with pinene or with oils rich in pinene, notably turpentine, and thereafter removing the mixtures of bornyl esters by distillation in vacuo.

It is found for example that when inene or oil of turpentine is heated at 160 .165 C. for 1216 hours with one half its weight of the ketonic acid mixture resulting from the condensation of gasoline and phthalic anhydride, that chemical combination occurs. The organic acid mixture goes rapidly into solution and reacts with the unsaturated bond of the pinene to form a complex mixture of bornyl esters. Any unchanged organic acid 'is then removed by washing with soda solution, and the remaining oil is fractionated in vacuo. At first turpentine comes over, then a small intermediate fraction of higher terpenes. A heavy, brown plastic mass remains behind in the still. It is distilled in vacuo to separate it from tarry by-products and comes over as an amber colored transparent, plastic mass that boils within the approximate range of 260 to 290 C. at 5 in. In.

ressure. It is a neutral compound possessing an odor of pine wood. It is readily soluble in toluol, butyl acetate, glycol ethers, acetone, alcohol and other organic solvents. It is readily compatible with nitrocellulose and acetyl cellulose, giving therewith clear films of excellent flexibility, adhesion, and

gloss. When boiled with strong alkalies the plastic mass is hydrolyzed forming borneol and soaps of the organic ketonic acid. The borneol may be isolated in the usual manner by steam distillation.

I have also condensed in an analogous manner, pinene or oil of turpentine with the'vari- 0115 other ketonic acids mentioned above, namely the monobasic acids obtained from the condensation of phthalic anhydride with kerosene, naphthas (Varsol, Varnoline, VM&P Naphtha, white spirit,) parafiin wax, parafiin oils (Nujol) lubricating oils and petrolatum, respectively; and have in each case obtained high boiling resinous esters which difi'er in physical properties from each other according to the nature of the hydrocarbons employed. In all cases, the esters boil above 250 C. at 5 m. m. pressure and form transparent very viscous sirups. I have noticed that as the molecular Weight of the petroleum hydrocarbon is increased, and group R- becomes larger, that the bornyl esters become progressively more waxy and less sticky in nature.

The ketonic acids which are formed by condensing maleic anhydride or suecinic anhydride with gasoline, kerosene, naphthas and other petroleum hydrocarbons in the presence of aluminum chloride, as described in my co-pending patent application Serial No. 398,823, are not quite as suitable as those derived from phthalic anhydride, for use in preparing resinous bornyl esters, as they combine more slowly with turpentine or pinene and tend to give liquid bornyl esters rather than plastic solids. However, they may be used either alone or in conjunction with phthalic anhydride to produce mixed bornyl esters having more fluid properties.

Instead of turpentine or pinene, camphene may be similarly heated with any of the above mentioned organic ketonic acids derived from petroleum hydrocarbons. The condensation may be carried out at higher or lower temperatures than those indicated by heating under pressure or in vacuo. Dehydrating catalysts such as boric oxide, zinc chloride and the like may be used to assist in the condensation.

What I claim is:

1. As a new composition of matter, the reaction product of a member of the group consisting of pinene, turpentine, and camhene, with the organic acids obtained by hydrolysis from the condensation product of an essentially non-aromatic petroleum oil hydrocarbon, a Friedel-Crafts type of metal halide catalyst, and the anhydride of a polycarboxylic acid.

2. A new composition of matter comprising the mixed bornyl esters of the organic acids which are obtained by hydrolysis from the condensation product of a petroleum hydrocarbon fraction substantially free of aromatic hydrocarbons, with a Friedel-Crafts type of metal halide catalyst, and the anhydride of a polycarboxylic acid.

3. As a new composition of matter, the reaction product of a member of the group consisting of pinene, turpentine, and camphene, with the organic acids obtained by hydrolysis from the condensation product of an essentially non-aromatic petroleum oil hydrocarbon, anhydrous aluminum chloride, and the anhydride of a polycarboxylic acid.

4. As a new composition of matter, the reaction product of a member of the group consisting of pinene, turpentine, and camphene, with the organic acids obtained by hydrolysis from the condensation product of an essentially non-aromatic petroleum oil hydrocarbon, anhydrous aluminum chloride and phthalic anhydride.

5. A new composition of matter comprising the reaction product of turpentine with the organic acids obtained by hydrolysis from the condensation product of a member of the group consisting of gasoline, petroleum, kerosene, naphtha, paraifin oil, petrolatum and paraflin wax with a Friedel-Crafts type of metal halide catalyst, and the anhydride of a polycarboxylic acid.

6. A new composition of matter comprising the reaction product of turpentine with the organic acids obtained by hydrolysis from the condensation product of gasoline, phthalic anhydride, and anhydrous aluminum chloride.

7. A new composition of matter comprising the reaction product of turpentine with the organic acids obtained by hydrolysis from the condensation product of petroleum naphtha, phthalic anhydride, and anhydrous aluminum chloride.

8. A new composition of matter comprising the reaction product ofturpentine with the organic acids obtained by hydrolysis from the condensation oil, phthalic anhydride, minum chloride.

9. A new composition of matter comprising the mixed bornyl esters of the organic acids obtained by hydrolysis from the condensation of a member of the group consisting of gasoline, kerosene, petroleum, naphtha, paraflin oil, petrolatum and parafiin wax with a Friedel-Crafts t pe of metal halide catalyst and the anhydride of a polycarboxylic acid.

10. A new composition of matter comprising the mixed bornyl esters of the Organic acids obtained by hydrolysis from the condensation product of a petroleum hydrocarbon substantially free of aromatic hydrocarbons, with anhydrous, aluminum chloride and phthalic anhydride.

11. In the process of preparing a mixed bornyl ester the step which comprises heating at reaction temperature, one of the group consisting of turpentine, pinene and camphene with the organic acid mixture obtained by hydrolysis from the condensation product of an essentially non-aromatic petroleum hydrocarbon, a Friedel-Crafts type of metal halide catalyst, and the anhydride of a polycarboxylic acid.

12. In the process for preparing a mixed bornyl ester of the type set forth in claim 11, the step which comprises a subsequent re moval of excess terpenes from the reaction mixture and isolation of the mixed bornyl esters by distillation in Vacuum.

13. A method for preparing a mixed bornyl ester which comprises heating turpentine at reaction temperature with the organic acids obtained from the hydrolysis of a condensation product of an essentially nonaromatic petroleum hydrocarbon, anhydrous aluminum chloride and phthalic anhydride; thereafter removing excess terpenes and any unchanged acidic material, and finally distilling the product in vacuum.

14. A new composition of matter comprising a terpene ester of the organic acids obtained by hydrolysis from the condensation product of an essentially nonaromatic petrolcum oil. hydrocarbon, a ldriedeLCrafts type of metal halide catalyst, and the anhydride of a polycarboxylic acid.

15. A new composition of matter comprising a terpene ester of the organic acids obtained by hydrolysis from the condensation product of a member of the group of gasoline, petroleum, kerosene, naphtha, parafin oil, petrolatum and paraihn wax with anhydrous aluminum chloride and phthalic anhydride,

HER A. BRUSQN.

product of paraflin and anhydrous alu- 

